JP2015230801A - Lithium air battery - Google Patents

Lithium air battery Download PDF

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JP2015230801A
JP2015230801A JP2014115987A JP2014115987A JP2015230801A JP 2015230801 A JP2015230801 A JP 2015230801A JP 2014115987 A JP2014115987 A JP 2014115987A JP 2014115987 A JP2014115987 A JP 2014115987A JP 2015230801 A JP2015230801 A JP 2015230801A
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lithium
air
gel polymer
electrolyte
polymer electrolyte
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JP6216288B2 (en
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政彦 林
Masahiko Hayashi
政彦 林
正也 野原
Masaya Nohara
正也 野原
薫 朝倉
Kaoru Asakura
薫 朝倉
博人 北林
Hiroto Kitabayashi
博人 北林
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日本電信電話株式会社
Nippon Telegr & Teleph Corp <Ntt>
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/128Hybrid cells composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type

Abstract

PROBLEM TO BE SOLVED: To provide a safe lithium air battery which is small in the decline in electrolyte owing to volatilization, and is arranged so that the battery can operate with stability over a long period of time.SOLUTION: A lithium air battery comprises: an air electrode including a conductive material and a catalyst; a negative electrode including metallic lithium or a lithium-containing substance; and a lithium ion-conducting electrolyte in contact with the air electrode and the negative electrode. The lithium ion-conducting electrolyte includes: a lithium ion-conducting organic electrolytic solution; and a lithium ion-conducting gel polymer electrolyte. The lithium ion-conducting gel polymer electrolyte covers a face of the air electrode on the side opposite to a face which is in contact with the air.

Description

  The present invention relates to a lithium air battery. In particular, the present invention relates to a lithium-air battery that is smaller and lighter than a conventional battery such as a lead-acid battery or a lithium-ion battery and that can achieve a discharge capacity that is much larger.

  Lithium-air batteries use oxygen in the air as a positive electrode active material, oxygen is always supplied from the outside of the battery, and a large amount of metallic lithium, which is a negative electrode active material, can be filled in the battery. For this reason, it has been reported that the value of the discharge capacity per unit volume of the battery can be greatly increased.

For example, in Non-Patent Document 1, electrolysis is performed using 1 mol / l lithium hexafluorophosphate (LiPF 6 ) as a solute and a mixed solvent of propylene carbonate (PC) and 1,2-dimethoxyethane (DME) as an organic solvent. The liquid is prepared and the lithium air (oxygen) battery is evaluated.

The electrolyte solution of Non-Patent Document 2 uses 1.0 mol / l LiPF 6 as a solute, and a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (30:70 by volume) as an organic solvent. Based on the above, it is prepared by mixing a small amount of tris (pentafluorophenyl) borane (TPFPB) as an additive for improving the cycle performance. Any literature reports that lithium-air batteries using these as electrolytes operate as air batteries and can improve large discharge capacity and cycle performance.

  However, since the organic solvent used in these documents is volatile, it is considered that there is a problem in stability in operating for a long time in a lithium air battery having a structure in which air is taken into the battery. . That is, when the battery is operated for a long period, it is expected that the battery resistance increases due to volatilization of the electrolytic solution from the positive electrode side, and the battery performance is significantly reduced. In fact, these documents only describe the results of only a few cycles. Moreover, since these organic electrolytes are volatile and flammable, there is a concern about safety such as fire accidents.

J. et al. Read et al. , Journal of The Electrochemical Society, Vol. 150, pp. A1351-A1356 (2003). N. -S. Choi et al. , Journal of Power Sources, Vol. 225, pp. 95-100 (2013).

  An object of the present invention is to provide a safe lithium-air battery in which the electrolyte does not decrease due to volatilization and the battery can be stably operated for a long time.

The present invention is for solving the above problems,
An air electrode containing a conductive material and a catalyst;
A negative electrode comprising lithium metal or a lithium-containing material;
A lithium-air battery comprising a lithium ion conductive electrolyte in contact with the air electrode and the negative electrode;
The lithium ion conductive electrolyte includes a lithium ion conductive organic electrolyte and a lithium ion conductive gel polymer electrolyte, and the lithium ion conductive gel polymer electrolyte has a surface opposite to a surface in contact with air of the air electrode. It is characterized by covering.

  In the lithium-air battery of the present invention, the lithium ion conductive gel polymer electrolyte preferably contains dimethyl sulfoxide (DMSO) or tetraethylene glycol dimethyl ether (TEGDME).

  In the lithium-air battery of the present invention, the lithium ion conductive gel polymer electrolyte has a thickness of 2 μm to 20 μm and covers a surface opposite to the surface of the air electrode that contacts the air.

  In the lithium air battery of the present invention, the lithium ion conductive gel polymer electrolyte includes an inorganic metal oxide filler.

  In the lithium-air battery of the present invention, the gel polymer electrolyte covers the surface opposite to the surface in contact with the air of the air electrode, whereby the above-described problems are improved. Moreover, the performance is improved by having the said structure of the lithium air battery of this invention. Furthermore, the gel polymer electrolyte contains an inorganic metal oxide filler, whereby the strength of the gel polymer electrolyte is improved and the performance is further improved.

  The lithium-air battery of the present invention is a high-energy density lithium-air battery with a small decrease in discharge capacity even after repeated many charge / discharge cycles.

It is a figure which shows the basic composition of the lithium air battery which concerns on this invention. It is a figure showing the synthesis method of the gel polymer electrolyte which concerns on this invention. It is the schematic which shows the structure of the coin-type lithium air battery cell which concerns on this invention. It is a figure which shows the charging / discharging curve of the lithium air battery cell which concerns on Example 1 and 3. FIG.

  Hereinafter, an embodiment of a lithium-air battery according to the present application will be described in detail with reference to the drawings as appropriate.

[Configuration of lithium-air battery]
The lithium-air battery according to the present invention includes an air electrode containing a conductive material and a catalyst, a negative electrode containing metallic lithium or a lithium-containing substance, and a lithium ion conductive electrolyte in contact with the air electrode and the negative electrode. One embodiment of the present invention is a lithium-air battery having a structure as shown in FIG. 1, and shows a basic configuration during discharge of the lithium-air battery according to the present invention.

  As shown in FIG. 1, a lithium-air battery 100 according to the present invention includes an air electrode (positive electrode) 102 containing a conductive material and a catalyst, a negative electrode (104) containing metallic lithium or a lithium-containing substance, and the air electrode In the lithium-air battery of the present invention, the electrolyte includes a lithium ion conductive gel polymer electrolyte 110 containing at least a lithium ion conductive organic electrolyte solution, and the gel polymer The electrolyte has a structure that covers the surface of the air electrode opposite to the surface in contact with the air, and the present invention may further include an electrolyte solution (for example, an organic electrolyte solution) 106, a separator 108, and the like. In addition, the separator 108 can be impregnated with an electrolytic solution.

  The air electrode 102 may include a catalyst and a conductive material as components. The air electrode preferably contains a binder for integrating the materials. The negative electrode 104 can be composed of a material such as a lithium-containing alloy capable of releasing and absorbing metallic lithium or lithium ions. The lithium ion conductive electrolyte will be described in detail below.

  Each of the above components will be described below. In the present specification, the electrolytic solution refers to a case where the electrolyte is in a liquid form.

(I) Air electrode (positive electrode)
In the present invention, the air electrode includes at least a catalyst and a conductive material, and may include additives such as a binder as necessary.

(I-1) Conductive Material In the present invention, the air electrode can contain a conductive material. An example of the conductive material is carbon. Examples of the carbon species used include carbon blacks such as ketjen black and acetylene black, activated carbons, graphites, carbon fibers, carbon cloths, and carbon sheets. In order to secure sufficient reaction sites in the air electrode, carbon having a large specific surface area is suitable. Specifically, a material having a BET specific surface area of 300 m 2 / g or more is desirable. These carbons can be obtained, for example, as commercial products or by known synthesis.

(I-2) Catalyst A highly active catalyst for oxygen reduction and oxygen generation reaction is added to the air electrode. Examples of the catalyst include oxides containing at least one of transition metals such as Mn, Fe, Co, Ni, V, and W. Specifically, single oxides such as MnO 2 , Mn 3 O 4 , MnO, FeO 2 , Fe 3 O 4 , FeO, CoO, Co 3 O 4 , NiO, NiO 2 , V 2 O 5 , WO 3 , La 0.6 Sr 0.4 MnO 3 , La 0.6 Sr 0.4 FeO 3 , La 0.6 Sr 0.4 CoO 3 , La 0.6 Ca 0.4 CoO 3 , P r0.6 Ca 0 Examples include composite oxides having a perovskite structure such as .4 MnO 3 , LaNiO 3 , La 0.6 Sr 0.4 Mn 0.4 Fe 0.6 O 3, and the like.

  As a synthesis method of these catalysts, known processes such as a solid phase method and a liquid phase method can be used. In the present invention, it is desirable to use a liquid phase method typified by a method of obtaining an amorphous precursor by evaporating and drying a mixed aqueous solution of metal acetate or metal nitrate or hydrolysis of metal alkoxide.

It is important for the catalyst to generate a large amount of three-phase interface sites on the surface of the catalyst particles, and the catalyst to be used preferably has a high surface area, and preferably has a BET specific surface area of 10 m 2 / g or more.

  Examples of the catalyst include macrocyclic metal complexes such as porphyrin or phthalocyanine containing at least one of transition metals such as Mn, Fe, Co, Ni, V, and W as a central metal. The activity of these metal complexes is increased by performing heat treatment in an inert gas atmosphere after mixing with carbon.

Examples of catalysts that can be used in the present invention include, in addition to the above examples, noble metals such as Pt, Au, Pd, and Ru, and noble metal-containing oxides such as palladium oxide (PdO) and ruthenium oxide (RuO 2 ). it can. Furthermore, transition metals such as Co, Ni, and Mn can also be cited as examples of the air electrode catalyst.

  The above-mentioned metal can express high activity by being supported on carbon with high dispersion. Specifically, high dispersibility can be achieved by dispersing or dispersing the carbon in a colloidal solution in which these metals are dispersed and adsorbing or supporting the metal particles on the carbon.

  In addition, a precious metal oxide containing carbon can be synthesized by performing heat treatment after adsorbing or supporting a metal on the carbon.

  In the lithium-air battery of the present invention, as described above, the specific surface area of the catalyst and carbon used for the air electrode preferably has a predetermined value. In the present invention, the specific surface area can be measured using a commercially available apparatus. For example, the specific surface area can be measured by a procedure using liquid nitrogen as a cooling medium using a commercially available measuring device.

(I-3) Binder (binder)
The air electrode can contain a binder (binder). The binder is not particularly limited, and examples thereof include polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVdF), and styrene butadiene rubber (SBR). . These binders can be used as a powder or as a dispersion.

  In the present invention, there are no particular limitations on the ratio of the conductive material, catalyst, and optional binder used in the air electrode. The usage rate of the air electrode used with a normal lithium air battery can be applied. For example, in the lithium-air battery of the present invention, the catalyst content in the air electrode is 0.5 to 50% by weight, the conductive material is 10 to 60% by weight, and the binder is 0 to 0%. 40% by weight.

(I-4) Preparation of air electrode An air electrode can be prepared as follows. For example, the air electrode can be formed by mixing the catalyst powder, carbon powder, and, if necessary, binder powder and pressing the mixture onto a support such as titanium mesh. Moreover, an air electrode can be formed by disperse | distributing the above-mentioned mixture in solvents, such as an organic solvent, and making it into a slurry form, apply | coating on a metal mesh or a carbon cloth, or a carbon sheet, and drying.

  One side of the obtained air electrode is exposed to the atmosphere, and the other side is in contact with the electrolyte. Moreover, in order to increase the strength of the electrode and prevent leakage of the electrolytic solution, an air electrode with more stability can be produced by applying not only a cold press but also a hot press.

(II) Negative electrode The lithium-air battery of the present invention contains a negative electrode active material in the negative electrode. The negative electrode active material is not particularly limited as long as it is a material that can be used as a negative electrode material for a lithium battery. For example, metallic lithium can be mentioned. Alternatively, examples of the lithium-containing substance include lithium and silicon or tin alloy, or lithium nitride such as Li 2.6 Co 0.4 N, which is a substance that can release and occlude lithium ions. be able to.

  In addition, when using said silicon or tin alloy as a negative electrode, the silicon | silicone or tin etc. which do not contain lithium can also be used when synthesize | combining a negative electrode. However, in this case, prior to the production of the air battery, a chemical method or an electrochemical method (for example, a method in which an electrochemical cell is assembled and lithium and silicon or tin are alloyed) is used to form silicon or silicon. It is necessary to treat so that tin is in a state containing lithium. Specifically, it is preferable that the working electrode contains silicon or tin, the counter electrode is lithium, and a treatment such as alloying is performed by flowing a reducing current in the organic electrolyte.

  The negative electrode of the lithium-air battery of the present invention can be formed by a known method. For example, when lithium metal is used as the negative electrode, the negative electrode may be produced by stacking a plurality of metal lithium foils into a predetermined shape.

(III) Electrolyte The electrolyte according to the present invention includes a lithium ion conductive organic electrolyte and a lithium ion conductive gel polymer electrolyte (in this specification, the lithium ion conductive gel polymer electrolyte is also simply referred to as a gel polymer electrolyte or a gel electrolyte). including. In the present invention, the gel polymer electrolyte is disposed on the surface of the air electrode opposite to the surface in contact with the air. The lithium ion conductive gel polymer electrolyte of the present invention includes the gel polymer and an electrolyte such as an organic electrolyte.

  Specifically, as shown in FIG. 1, the electrolyte includes a gel polymer electrolyte 110 and an electrolytic solution (preferably an organic electrolytic solution) 106, which are disposed between the air electrode 102 and the negative electrode 104. If necessary, the electrolytic solution 106 may be disposed by means of impregnating the separator 108.

  In order to prevent the electrolytic solution 106 from volatilizing, the gel polymer electrolyte 110 is preferably disposed so as to cover the entire surface of the air electrode opposite to the surface in contact with the air.

  The gel polymer electrolyte can be prepared, for example, by the procedure shown in FIG. First, polymer particles such as PVdF are dissolved in a tetrahydrofuran (THF) solvent while heating as necessary (202 to 206). Next, an organic electrolytic solution is added to this solution (208), and further mixed while heating (210) as necessary. The obtained solution is cast on a glass plate such as a petri dish by dropping it with a dropper (212), heat-treated and dried (214 to 216) to produce a membrane gel polymer electrolyte. Can do. The obtained film-like gel polymer electrolyte is molded, added with an organic electrolyte, and impregnated as necessary (218 to 224).

The organic electrolyte contained in the gel polymer electrolyte is not particularly limited as long as it is used for a lithium battery. For example, a metal salt containing a lithium ion such as lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium perchlorate (LiClO 4 ), or lithium hexafluorophosphate (LiPF 6 ) dissolved in a solvent may be mentioned. it can. In the present invention, the solvent is preferably a non-aqueous solvent such as a dimethyl sulfoxide (DMSO) solvent or a tetraethylene glycol dimethyl ether (TEGDME) solvent that has low reactivity with oxygen in the air and is unlikely to deteriorate.

  The gel polymer electrolyte coats the surface of the air electrode opposite to the surface in contact with the air. Therefore, in order to uniformly coat the gel polymer electrolyte on the entire surface of the air electrode, the gel polymer electrolyte needs to have a certain thickness. If the film thickness is too large, it becomes a barrier when conducting lithium ions, so it is necessary to suppress the film thickness to some extent. Specifically, the film thickness of the gel polymer electrolyte is desirably in the range of 2 μm to 20 μm.

  In the present invention, an air electrode coated with the gel polymer electrolyte can be created by forming the gel polymer electrolyte into a predetermined shape that matches the shape of the air electrode and pressing the gel polymer electrolyte onto the air electrode. For example, a gel polymer electrolyte sheet can be prepared by the procedure as described above, and can be placed on the target surface of the air electrode by pressure bonding so as to cover the entire target surface of the air electrode.

  As a method of coating the gel polymer electrolyte on the entire target surface of the air electrode in addition to the above-described pressure-bonding of the gel polymer electrolyte sheet to the air electrode, there is a method such as a spin coating method.

Furthermore, the gel polymer electrolyte may further include an inorganic metal oxide filler such as Al 2 O 3 or SiO 2 . By including such an inorganic filler, when the gel polymer electrolyte is coated on a predetermined surface of the air electrode, the strength is improved, and the performance of the lithium-air battery of the present invention is further improved.

  The content of the inorganic metal oxide filler in the gel polymer electrolyte is preferably 2 to 50% by weight based on the total weight of the gel polymer electrolyte.

  In the present invention, the electrolyte includes an organic electrolyte (for example, an organic electrolytic solution) in addition to the gel polymer electrolyte. When the organic electrolyte is an organic electrolyte, a separator or the like may be impregnated.

The organic electrolyte is not particularly limited as long as it is used for a lithium battery. For example, metal salts containing lithium ions such as lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), for example, ethylene carbonate (EC) and dimethyl carbonate Nonaqueous organic electrolysis dissolved in a mixed solvent of (DMC), a mixed solvent such as EC and diethyl carbonate (DEC), or a single solvent such as propylene carbonate, dimethyl sulfoxide (DMSO), tetraethylene glycol dimethyl ether (TEGDME) A liquid etc. can be mentioned as an example.

  In the present invention, the organic electrolytic solution used for the gel polymer electrolyte 110 and the organic electrolyte 106 may be the same or different. For example, 1 mol / l LiTFSI / TEGDME or 1 mol / l LiTFSI / DMSO can be used for the organic electrolyte used for the gel polymer electrolyte 110, and 1 mol / l LiTFSI / PC can be used for the organic electrolyte 106.

(IV) Other Elements In addition to the above-described components, the lithium-air battery of the present invention includes structural members such as separators, battery cases, metal meshes (for example, titanium mesh), and other elements required for lithium-air batteries. Can do. Conventionally known ones can be used.

(V) Production of Lithium-Air Battery The lithium-air battery of the present invention includes at least an air electrode (positive electrode), a negative electrode, and an electrolyte as described above. For example, as shown in FIG. 1, the electrolyte is sandwiched between the air electrode and the negative electrode, and the surface of the air electrode opposite to the surface in contact with air is coated with the gel polymer electrolyte. . The lithium air battery having such a configuration can be manufactured by a conventional procedure. For example, an air electrode, a negative electrode, and an electrolyte are prepared, stacked in a predetermined order, and housed in a battery case as necessary. Moreover, the coating method to the air electrode of a gel polymer electrolyte is as above-mentioned, For example, what is necessary is just to press-fit with the air electrode which shape | molded the gel polymer electrolyte formed in the film form in the predetermined shape.

  In one embodiment, for example, a coin-type lithium-air battery as shown in FIG. 3 can be manufactured. As shown in FIG. 3, the coin cell type air battery includes at least an air electrode 306, a gel electrolyte 308, a separator 310 impregnated with an electrolytic solution, and a negative electrode 312. Further, the air battery may include a cathode case 302, a titanium mesh 304, a Ni mesh 314, a spacer 316, a wave washer 318, an anode case 320, and the like. The air battery includes, for example, an air electrode / gel polymer electrolyte obtained by lightly pressing an air electrode 306 and a gel polymer electrolyte 308, a separator 310 impregnated with the organic electrolyte, a negative electrode 312 containing metallic lithium or a lithium-containing substance, and Each of the other elements described above can be manufactured by stacking in the order shown in FIG. 3, placing them in the cathode case 302 and the anode case 320, and fixing both cases on which the respective components are placed. Commercially available products can be used as the separator and battery cell case.

  Embodiments of a lithium-air battery according to the present invention will be described below in detail with reference to the accompanying drawings. In addition, this invention is not limited to what was shown to the following Example, In the range which does not change the summary, it can change suitably and can implement.

(Examples 1-4)
(I) Production of Gel Polymer Electrolyte Membrane A gel polymer electrolyte membrane was produced by the method shown in FIG. In this example, a sample containing PVdF and 1 mol / l LiTFSI / TEGDME electrolytic solution or PVdF and 1 mol / l LiTFSI / DMSO electrolytic solution was prepared.

  Specifically, as shown in FIG. 2, PVdF particles (manufactured by Aldrich) are dissolved in a tetrahydrofuran (THF) solvent while heating at 60 ° C., and an organic electrolyte [1 mol / l LiTFSI / TEGDME or 1 mol / l LiTFSI / DMSO, both reagents manufactured by Toyama Pharmaceutical Co., Ltd.] were added and dissolved while heating at 60 ° C. The obtained solution was dropped into a glass plate such as a petri dish using a dropper, and further vacuum dried at 90 ° C. for 3 hours. Thereafter, the obtained sheet was gradually cooled to obtain a film-like gel polymer electrolyte. Furthermore, in order to fill the fine voids of the prepared gel polymer electrolyte, the electrolyte membrane was impregnated with an electrolytic solution having the same composition as the organic electrolytic solution, and then the excess electrolytic solution was wiped off. This obtained the film-form gel polymer electrolyte without a space | gap. The film thickness could be adjusted by adjusting the amount of dripping onto the petri dish.

  The composition of the gel polymer electrolyte was electrolytic solution: PVdF = 80: 20 (weight ratio). The obtained gel polymer electrolyte was cut out into a circle having a diameter of 17 mm using a metal punch. In Examples 1 to 4, gel polymer electrolytes having different film thicknesses as shown below were produced.

(II) Production of air electrode Commercially available ruthenium oxide (RuO 2 ) powder (manufactured by Kanto Chemical), Ketjen black EC600JD powder (manufactured by Lion Corporation, BET specific surface area 1270 m 2 / g) and polytetrafluoroethylene (PTFE) The powder was sufficiently pulverized and mixed using a rake machine at a weight ratio of 5:57:38, and roll-formed to produce a sheet-like electrode (thickness: 0.5 mm). The sheet electrode was cut into a circle having a diameter of 13 mm and pressed onto a titanium mesh to obtain a gas diffusion type air electrode. The air electrode thus produced and the gel polymer electrolyte were lightly pressure-bonded with the center aligned, to obtain an air electrode / gel polymer electrolyte structure.

(III) Production of Organic Electrolyte Impregnated Separator A sufficient amount of commercially available organic electrolyte 1 mol / l LiTFSI / PC (manufactured by Toyama Pharmaceutical Co., Ltd.) was applied to a commercially available PE separator (Celgard, diameter 17 mm). Impregnated. After leaving still for 2-3 hours, the excess electrolyte solution was wiped off from the separator using Kimwipe. The organic electrolyte-impregnated separator was prepared by the above procedure.

(IV) Production of Metal Lithium Negative Electrode Three commercially available metal lithium foils (thickness 0.2 mm, diameter 13 mm, manufactured by Honjo Metal Co., Ltd.) were stacked with the centers aligned and lightly pressed to produce a negative electrode.

(V) Production of Air Battery Cell FIG. 3 shows a stacked structure of coin-type lithium air battery cells. As shown in FIG. 3, after laminating each component including the elements created as described above, the case is crimped using a commercially available caulking machine (manufactured by Hosen Co., Ltd.), thereby coin-type lithium air A battery cell was obtained. The battery was produced in dry air having a dew point of −60 ° C. or less.

(VI) Battery performance evaluation The charge / discharge cycle test of the battery was performed with a current density per effective area of the air electrode (area directly exposed to air) using a charge / discharge measurement system (BioLogic VMP-3). 0.1 mA / cm 2 was energized, and the discharge voltage was measured until the battery voltage dropped from the open circuit voltage to 2.0V. Subsequently, the charge was measured at the same current density so that a cutoff of 4.2 V or a discharge time = charge time. Moreover, this cycle was repeated and the battery performance was evaluated. The battery discharge test was performed in a normal living environment. The charge / discharge capacity was expressed as a value (mAh / g) per weight of air electrode (carbon + oxide + PTFE).

  FIG. 4 shows initial discharge and charge curves of the air battery cells of Examples 1 and 3 in which the gel polymer electrolyte is applied to the air electrode with a film thickness of 2 μm. Both examples showed large discharge capacities exceeding 1000 mAh / g, but Example 3 using DMSO showed a value about 1.3 times larger than Example 1 using TEGDME. Regarding the operating voltage, the average discharge voltage was almost the same in both Examples, but regarding charging, Example 3 using DMSO could be charged at a low voltage. Thus, although the behavior was different depending on the organic electrolyte contained in the gel polymer electrolyte, it was confirmed that both examples had a large discharge capacity. Table 2 summarizes the discharge capacities at the first, 50th and 100th cycles. Both Examples 1 and 3 exhibited relatively stable cycle performance, and the capacity retention rate after 150 cycles was a high value of about 80%.

  Table 2 summarizes the discharge capacities of the first, 50th and 100th cycles of the air battery cells of Examples 2 and 4 in which the gel polymer electrolyte was applied to the air electrode with a film thickness of 20 μm thicker than those of Examples 1 and 3. Show. From Table 2, it was found that Examples 2 and 4 had a smaller overall capacity than Examples 1 and 3. This is presumably because the resistance of the entire cell increased due to the increase in film thickness. However, both examples showed a discharge capacity of 1000 mAh / g or more at the first time, and the discharge capacity retention rate when the cycle was repeated was the same as in Examples 1 and 3.

  From these results, it was confirmed that the present invention in which the gel polymer electrolyte is applied to the air electrode surface is an effective technique for obtaining battery performance of a large discharge capacity and excellent cycle stability.

(Examples 5 and 6)
In this example, an inorganic oxide filler is added to the gel polymer electrolyte.

Al 2 O 3 (manufactured by Kanto Chemical Co., Ltd.) or SiO 2 (manufactured by Kanto Chemical Co., Ltd.) was added to the gel polymer electrolyte as an inorganic oxide filler with the gel polymer electrolyte composition shown in Table 3. As the organic electrolyte, 1 mol / l LiTFSI / DMSO was used.

  The production of the lithium-air battery is almost the same as that in the above example. That is, in 208 of FIG. 2, an inorganic oxide was mixed with the organic electrolyte solution, subjected to ultrasonic treatment so as to be well dispersed, and then mixed with the PVdF solution (202 to 210). The subsequent steps are as shown in FIG. The production of the air electrode and the production of the air battery cell were performed in the same manner as in Examples 1 to 4.

  Table 2 summarizes the discharge capacities of the first, 50th, and 100th cycles of Examples 5 and 6. Compared to Example 3 in which no filler was used, although a slight capacity decrease was observed in the first discharge, the cycle stability was excellent, and both examples had a high capacity maintenance rate of about 87% even after 150 cycles. Indicated. This is presumably because the addition of the filler improved the strength of the gel polymer electrolyte and promoted the effect of preventing the electrolyte from volatilizing.

(Comparative example)
In order to verify the effectiveness of the present invention, the following air battery cells were produced.

(Comparative Example 1)
An air battery cell containing no gel polymer electrolyte, that is, containing only an organic electrolyte (1 mol / l LiTFSI / PC) impregnated in the separator was produced.

(Comparative Example 2)
An air battery cell using a gel polymer electrolyte [organic electrolyte (1 mol / l LiTFSI / DMSO): PVdF = 80: 20 (weight ratio)] having a film thickness of 1 μm deviating from the film thickness of the preferred gel polymer electrolyte of the present invention. Produced. In addition, 1 mol / l LiTFSI / PC was used as the organic electrolyte solution impregnated in the separator.

(Comparative Example 3)
An air battery cell using a gel polymer electrolyte [organic electrolyte (1 mol / l LiTFSI / DMSO): PVdF = 80: 20 (weight ratio)] having a film thickness of 21 μm deviating from the film thickness of the preferred gel polymer electrolyte of the present invention. Produced. In addition, 1 mol / l LiTFSI / PC was used as the organic electrolyte solution impregnated in the separator.

  Air electrode production and cell production were performed by the same methods as in Examples 1 to 4. Table 2 shows the battery performance of the lithium-air battery according to this comparative example.

  In Comparative Example 1, although a large initial discharge capacity was shown, the capacity suddenly decreased when the cycle was repeated, and became zero after 23 cycles.

  Comparative Examples 2 and 3 exhibit more stable cycle characteristics than Comparative Example 1, but have a lower capacity retention rate than Examples 3 and 4 which are within the range of the preferred gel polymer electrolyte thickness of the present invention. I understood.

  From the above results, it was confirmed that the gel polymer electrolyte of the present invention greatly contributed to the realization of excellent battery performance. Moreover, it was confirmed that the gel polymer electrolyte in which the film thickness in the present invention is appropriately controlled functions effectively as a volatilization preventing film for the electrolytic solution and greatly contributes to the realization of excellent battery performance.

  The lithium-air battery of the present invention can drive a mobile device such as an electric car and a smartphone for a long time, or can greatly increase the operation of a backup system in the event of a power failure using the lithium-air battery of the present invention. It is thought that it can be prolonged for a long time.

  By using the configuration of the lithium-air battery according to the present invention, a high-energy density lithium-air battery excellent in charge / discharge cycle performance can be produced and effectively used as a drive source for electric vehicles and various electronic devices. Can do.

102 Air electrode (positive electrode)
104 Negative electrode 106 Organic electrolyte (organic electrolyte)
108 Separator 110 Gel polymer electrolyte 202, 204, 206, 208, 210, 212, 214, 216, 218, 220, 222, 224 Each step of manufacturing the gel polymer electrolyte 302 Cathode case 304 Ti mesh 306 Air electrode 308 Gel polymer electrolyte (Gel electrolyte)
310 Organic Electrolyte Impregnated Separator 312 Negative Electrode (Li Metal)
314 Ni mesh 316 Spacer 318 Wave washer 320 Anode case

Claims (4)

  1. An air electrode containing a conductive material and a catalyst;
    A negative electrode comprising lithium metal or a lithium-containing material;
    A lithium air battery comprising a lithium ion conductive electrolyte in contact with the air electrode and the negative electrode,
    The lithium ion conductive electrolyte includes a lithium ion conductive organic electrolyte and a lithium ion conductive gel polymer electrolyte, and the lithium ion conductive gel polymer electrolyte has a surface opposite to a surface in contact with air of the air electrode. Lithium air battery characterized by covering.
  2.   The lithium air battery according to claim 1, wherein the lithium ion conductive gel polymer electrolyte contains dimethyl sulfoxide (DMSO) or tetraethylene glycol dimethyl ether (TEGDME).
  3.   3. The lithium air battery according to claim 1, wherein the lithium ion conductive gel polymer electrolyte has a thickness of 2 μm to 20 μm and covers a surface of the air electrode opposite to the surface in contact with the air.
  4.   The lithium-air battery according to any one of claims 1 to 3, wherein the lithium ion conductive gel polymer electrolyte includes an inorganic metal oxide filler.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070117007A1 (en) * 2005-11-23 2007-05-24 Polyplus Battery Company Li/air non-aqueous batteries
JP2010061452A (en) * 2008-09-04 2010-03-18 Mobile Business Promote:Kk Terminal apparatus, information processing method, and program
JP2013098176A (en) * 2011-10-27 2013-05-20 Samsung Electronics Co Ltd Electrolyte for lithium air battery, and lithium air battery including the same
JP2013214383A (en) * 2012-04-02 2013-10-17 Sony Corp Air battery, use method of air battery, and electronic apparatus
JP2014504428A (en) * 2010-12-01 2014-02-20 ハイドロ−ケベック Lithium air battery
JP2014056822A (en) * 2012-09-13 2014-03-27 Samsung Electronics Co Ltd Lithium battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070117007A1 (en) * 2005-11-23 2007-05-24 Polyplus Battery Company Li/air non-aqueous batteries
JP2010061452A (en) * 2008-09-04 2010-03-18 Mobile Business Promote:Kk Terminal apparatus, information processing method, and program
JP2014504428A (en) * 2010-12-01 2014-02-20 ハイドロ−ケベック Lithium air battery
JP2013098176A (en) * 2011-10-27 2013-05-20 Samsung Electronics Co Ltd Electrolyte for lithium air battery, and lithium air battery including the same
JP2013214383A (en) * 2012-04-02 2013-10-17 Sony Corp Air battery, use method of air battery, and electronic apparatus
JP2014056822A (en) * 2012-09-13 2014-03-27 Samsung Electronics Co Ltd Lithium battery

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